CN110813072B - Novel integrated material for flue gas desulfurization, denitrification and CO removal, and preparation and application thereof - Google Patents
Novel integrated material for flue gas desulfurization, denitrification and CO removal, and preparation and application thereof Download PDFInfo
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- CN110813072B CN110813072B CN201911219684.3A CN201911219684A CN110813072B CN 110813072 B CN110813072 B CN 110813072B CN 201911219684 A CN201911219684 A CN 201911219684A CN 110813072 B CN110813072 B CN 110813072B
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- 239000000463 material Substances 0.000 title claims abstract description 116
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 72
- 230000023556 desulfurization Effects 0.000 title claims abstract description 72
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003546 flue gas Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000003197 catalytic effect Effects 0.000 claims abstract description 100
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 64
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 48
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 36
- 239000004568 cement Substances 0.000 claims abstract description 35
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 32
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 32
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 15
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000440 bentonite Substances 0.000 claims abstract description 5
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 5
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 3
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 3
- 239000010440 gypsum Substances 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 84
- 239000008367 deionised water Substances 0.000 claims description 60
- 229910021641 deionized water Inorganic materials 0.000 claims description 60
- 238000000354 decomposition reaction Methods 0.000 claims description 53
- 150000003839 salts Chemical class 0.000 claims description 24
- 238000002791 soaking Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 19
- 238000004898 kneading Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims 2
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 description 31
- 239000002245 particle Substances 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 20
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- 230000002378 acidificating effect Effects 0.000 description 13
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 9
- 238000005470 impregnation Methods 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 230000002153 concerted effect Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Inorganic materials [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8637—Simultaneously removing sulfur oxides and nitrogen oxides
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/864—Removing carbon monoxide or hydrocarbons
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- B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
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Abstract
The invention provides a novel integrated material for desulfurization, denitrification and CO removal of flue gas, and belongs to the technical field of flue gas purification. Comprises 30 to 80 portions of active component, 0.1 to 5 portions of catalytic component A, 0.1 to 5 portions of catalytic component B, 0.1 to 5 portions of auxiliary agent and 2 to 30 portions of carrier according to the weight portion; the active component is CaCO3With CaO, Ca (OH)2One or two of them; the catalytic component A is Fe2O3、Co3O4One or more of the above; the catalytic component B is MnO2、CuO、MoO3One or more of the above; the auxiliary agent is MgO and CeO2、BaO、TiO2One or more of the above; the carrier is one or more of kaolin, bentonite, gypsum and cement. The invention also provides a preparation method of the integrated new material for flue gas desulfurization, denitrification and CO removal. The invention has low cost of raw materials, good effects of desulfurization, denitrification and CO removal, and the use temperature of 100-250 ℃. The integrated new material for flue gas desulfurization, denitrification and CO removal is suitable for simultaneously removing SO from industrial exhaust gas such as blast furnace gas, converter gas and the like2、SO3、NOXAnd CO, which reaches the ultra-low emission standard.
Description
Technical Field
The invention belongs to the technical field of flue gas purification, and particularly relates to a novel integrated material for flue gas desulfurization, denitrification and CO removal, and preparation and application thereof.
Background
NOxAnd SO2Is one of the main atmospheric pollutants, causes a series of hazards such as acid rain, photochemical smog and the like, and seriously affects the ecological environment and human health. China is a big coal resource country, and flue gas generated by burning coal is more NOx and SO2Main source of emission, so reducing NOxAnd SO2The emission is the most important factor for pollution emission reduction in China. In addition, because the combustion is insufficient, a part of flue gas is not completely oxidized, the discharged flue gas contains part of CO, and the treatment of CO is gradually promoted along with the improvement of national emission standards. Aiming at the situation that a part of flue gas (such as blast furnace flue gas, converter flue gas, dry quenching tail gas and the like) simultaneously contains NOx、SO2And CO, there is currently no good solution, and there are fewer and fewer integrated removal solutions for these fumes.
Aiming at the technical field of integration of desulfurization, denitrification and CO removal, no good solution is available at present, and the method is a technical difficulty in overcoming the problems of scientific research workers at present.
Disclosure of Invention
The invention aims to solve the problem that the blast furnace flue gas, the converter flue gas and the dry quenching tail gas simultaneously contain NOx、SO2And under the condition of CO, provides an integrated new material for flue gas desulfurization, denitrification and CO removal, and preparation and application thereof.
The purpose of the invention is realized by the following technical scheme:
a novel integrated material for flue gas desulfurization, denitrification and CO removal comprises, by weight, 30-80 parts of an active component, 0.1-5 parts of a catalytic component A, 0.1-5 parts of a catalytic component B, 0.1-5 parts of an auxiliary agent and 2-30 parts of a carrier; the active component is CaCO3With CaO, Ca (OH)2One or two of them; the catalytic component A is Fe2O3、Co3O4One or more of the above; the catalytic component B is MnO2、CuO、MoO3One or more of the above; the auxiliary agent is MgO, BaO or CeO2、TiO2One or more of the above; the carrier is one or more of kaolin, bentonite, gypsum and cement.
Further, the catalyst comprises, by weight, 50-70 parts of an active component, 1-3 parts of a catalytic component A, 1-3 parts of a catalytic component B, 1-3 parts of an auxiliary agent and 10-20 parts of a carrier.
Further, the active component is CaCO3With CaO, or CaCO3And Ca (OH)2Or CaCO3With CaO, Ca (OH)2Mixtures of, CaCO3The mass percentage of the active components is 2-50%.
Catalytic component, SO, in the novel materials of the present application2In Fe2O3、Co3O4Is converted into SO under the action of catalytic oxidation3Converted SO3Dissolving in water film on the surface of active component, and reacting with active component Ca to obtain CaSO4Thereby achieving the desulfurization effect; NO in MnO2、CuO、MoO3Conversion to NO by catalysis2Converted NO2Dissolving in water film on the surface of active component, and reacting with active component Ca to generate Ca (NO)3)2Thereby achieving the denitration effect. CO in MnO2CuO is converted into CO under the action of catalytic oxidation2CO after conversion2Dissolving in water film on the surface of active component, and mixing with active component Ca (OH)2Or reaction of CaO to CaCO3Thereby achieving the effect of removing CO; wherein the auxiliary agent is used for modulating the electronic potentials of the catalytic component A and the catalytic component B, enhancing the catalytic function thereof through synergistic effect, and improving the SO resistance of the catalytic component2The poisoning effect improves the removal efficiency; the carrier is used for dispersing the active components, the catalytic components and the auxiliary agents, and is also a molding component.
A preparation method of a novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following steps:
1) dissolving the salt of the catalytic component A in deionized water, and uniformly soaking the salt in an active component CaCO3The active component CaCO loaded with the catalytic component A3Drying and heating for decomposition.
Specifically, the salt of the catalytic component A is dissolved in deionized water and evenly dipped in 100-mesh 300-mesh active component CaCO3On the CaC loaded with catalytic component AO3Drying for 1-3h at the temperature of 100-.
Further, the salt of the catalytic component A is nitrate or chloride, and the concentration of the salt of the catalytic component A dissolved in deionized water is 0.01-0.5 g/ml.
Further, the nitrate is Fe (NO)3)3·9H2O、Co(NO3)2·6H2And one or more of O.
Further, the impregnation is preferably an equal volume impregnation. The equal volume impregnation can ensure that the active center of the catalytic component A is at CaCO3Well dispersed, catalytic oxidation of SO by concerted catalysis2Thereby promoting SO2Oxidation-absorption-fixation.
2) Dissolving the salt of the catalytic component B into deionized water, and uniformly soaking the salt in active components CaO or Ca (OH)2Or CaO with Ca (OH)2The active component loaded with the catalytic component B is dried and decomposed by heating.
Specifically, the salt of the catalytic component B was dissolved in deionized water and uniformly impregnated with 100-mesh 300-mesh active component CaO or Ca (OH)2Or CaO with Ca (OH)2On the mixture of (1), CaO or Ca (OH) of catalytic component B2Or CaO with Ca (OH)2The mixture is dried for 1 to 3 hours at the temperature of 100 ℃ and 140 ℃ and then is put into a muffle furnace for decomposition at the temperature of 200 ℃ and 500 ℃ for 1 to 4 hours.
Further, the salt of the catalytic component is nitrate or chloride, and the concentration of the salt of the catalytic component dissolved in the deionized water is 0.01-0.5 g/ml.
Further, the nitrate is Mn (NO)3)2·4H2O、Cu(NO3)2·3H2O、Mo(NO3)3.5H2And one or more of O.
Further, the impregnation is preferably an equal volume impregnation. The equal volume impregnation can ensure that the active center of the catalytic component B is CaO or Ca (OH)2Or CaO with Ca (OH)2Are well dispersed on the mixture of (A) and act by concerted catalysisBy catalytic oxidation of NOXAnd CO, thereby promoting NOXAnd CO oxidation-absorption-fixation.
3) Adding water into the sample and the carrier prepared in the steps 1) and 2), kneading, extruding and molding, and drying.
Specifically, the samples prepared in the step 1) and the step 2) are uniformly mixed with a carrier with the granularity of 100-.
Furthermore, the sample is extruded and formed into a cylindrical strip shape or a plum blossom shape, the diameter is 3-6mm, and the length is 4-15 mm. Therefore, the efficiency of the integrated material for desulfurization, denitrification and CO removal under the working condition of lower bed resistance drop can be maintained in industrial application.
4) And (3) dissolving the salt of the auxiliary agent into deionized water, uniformly soaking the salt in the sample prepared in the step 3), and drying, heating and decomposing to prepare the integrated material for flue gas desulfurization, denitrification and CO removal.
Specifically, dissolving the salt of the auxiliary agent into deionized water, uniformly soaking the salt on the sample prepared in the step 3), drying the sample loaded with the auxiliary agent for 1-3h at the temperature of 100-140 ℃, and then putting the sample into a muffle furnace for decomposition at the temperature of 200-500 ℃ for 1-4 h.
Further, the auxiliary salt is nitrate or chloride, the titanium is titanyl sulfate, and the concentration of the auxiliary salt dissolved in deionized water is 0.01-0.5 g/ml.
Further, the nitrate is Ce (NO)3)3·6H2O、Mg(NO3)2.6H2O、Ba(NO3)2One or more of them.
Further, the impregnation is preferably an equal volume impregnation. The equal-volume impregnation can ensure that the auxiliary agent is well dispersed on a new material, the electronic potentials of the catalytic component A and the catalytic component B are adjusted and regulated by combining with the catalytic component A and the catalytic component B, the catalytic function of the catalytic component A and the catalytic component B is enhanced by the synergistic effect, and in addition, the SO resistance of the catalytic component is improved2Toxic action, extractHigh removal efficiency of new materials.
An application of a novel integrated material for flue gas desulfurization, denitrification and CO removal, wherein the novel material is applied to the flue gas desulfurization, denitrification and CO removal at low temperature of 100 ℃ and 250 ℃.
Further, the new material is placed in a fixed bed reactor or a moving bed reactor to desulfurize, denitrate and remove CO from the flue gas, and the operation conditions are as follows: 0-5MPa, 100 ℃ and a gas space velocity of 100--1。
Compared with the prior art, the invention has the following beneficial effects:
the novel material has the advantages of high desulfurization efficiency of more than 95%, high denitration efficiency of more than 90%, high CO removal efficiency of more than 90%, simultaneous removal effect and fixed investment saving.
The novel material adopts cheap Ca as the raw material of the active component and cheap metal oxide as the catalytic component and the auxiliary agent, thereby effectively reducing the preparation cost.
The active center of the catalytic component is modified by the aid of the auxiliary agent, the electronic structure of the catalytic component is modulated, and the catalytic function of the catalytic component is enhanced; meanwhile, the active centers of the catalytic components are dispersed, so that the active sites of the catalytic components are reduced due to the aggregation and growth of the active centers under the operating condition, and the operating stability is improved.
The preparation method of the new material of the invention simultaneously catalyzes and oxidizes SO2、NOXThe different catalytic components of CO are well combined in one material without impairing the respective catalytic effect.
The catalytic component A and CaCO are prepared by the step-by-step preparation method3The active components are prepared together to make SO2After oxidation can react with CaCO3Reaction to produce CaSO4Thereby avoiding SO2With CaO or Ca (OH)2The reaction reduces active components capable of removing NOx and CO, and avoids SO2、NOX、CO2Competitive absorption effects on the active ingredient. Catalytic component B with CaO or Ca (OH)2Or CaO with Ca (OH)2Can increase the NOx and CO oxidation-absorption effect.
According to the invention, the structure-activity relationship of the absorption active site (Ca), the catalytic active site and the auxiliary agent is constructed through structure regulation, so that the desulfurization, denitrification and CO removal performance of the integrated new material is enhanced.
Drawings
FIG. 1 shows a desulfurization, denitrification and CO removal performance evaluation reaction device;
reference numerals: 1-water storage tank, 2-plunger pump, 3-ball valve, 4-mass flowmeter, 5-pressure reducing valve, 6-mass flowmeter, 7-pressure reducing valve, 8-mass flowmeter, 9-pressure reducing valve, 10-mass flowmeter, 11-pressure reducing valve, 12-reactor, 13-condenser, 14-three-way ball valve, 15-ball valve and 16-needle valve.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co2O3(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (13 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 50g of 200 meshActive component Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 13g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 1 for desulfurization, denitrification and CO removal.
Example 2
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(20wt.％)，CaCO3(20wt.％)；
Catalytic component A and content: co3O4(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (48 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 20g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 15g of deionized water and uniformly immersed in 20g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 48g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40 wt% of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 2 for desulfurization, denitrification and CO removal.
Example 3
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: CaO (50 wt.%), CaCO3(25wt.％)；
Catalytic component A and content: co3O4(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (0 wt.%), cement (2 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2Dissolving the solution in 50g of deionized water, uniformly soaking the solution on 50g of 200-mesh active component CaO, drying the solution for 2 hours at the temperature of 110 ℃, and then putting the solution into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 2g of cement with the particle size of 200 meshes, adding deionized water accounting for 40 wt% of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 3 for desulfurization, denitrification and CO removal.
Example 4
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co3O4(0.5wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (14.5 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) 1.75g of Co (NO) was weighed3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 14.5g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading the mixture in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 4 for desulfurization, denitrification and CO removal.
Example 5
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: fe2O3(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (13 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) 10.1g of Fe (NO) was weighed3)3·9H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 13g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 5 for desulfurization, denitrification and CO removal.
Example 6
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co3O4(2wt.％)；
Catalytic component B and content: MnO2(0.5wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (14.5 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 2.1g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 14.5g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading the mixture in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 6 for desulfurization, denitrification and CO removal.
Example 7
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co3O4(2wt.％)；
Catalytic component B and content: CuO (2 wt.%);
auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (13 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 6.1g of 50% Cu (NO) was weighed3)2·3H2O, dissolved in 20g of deionized water and uniformly impregnated with 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 13g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 7 for desulfurization, denitrification and CO removal.
Example 8
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co3O4(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: TiO 22(0.5wt.％)；
Carrier and content: kaolin (15.3 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 15.3g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading the mixture in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 1.4g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 8 for desulfurization, denitrification and CO removal.
Example 9
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co3O4(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: MgO (3 wt.%);
carrier and content: kaolin (13 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 13g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) 19.2g of Mg (NO) was sampled3)2.6H2And O, dissolving in 10g of water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 9 for desulfurization, denitrification and CO removal.
Example 10
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co3O4(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: CeO (CeO)2(3wt.％)；
Carrier and content: kaolin (13 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 13g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) Taking 7.6g of Ce (NO)3)3·6H2And O, dissolving in 10g of water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 10 for desulfurization, denitrification and CO removal.
Example 11
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co3O4(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: bentonite (13 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 13g of bentonite with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40 wt% of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 11 for desulfurization, denitrification and CO removal.
Example 12
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co2O3(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (13 wt.%), cement (5 wt.%).
Shape: 6mm plum blossom-shaped column
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 13g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading in a kneader for 2 hours. The kneaded sample was extruded into a cylindrical plum-blossom shape with a diameter of 6mm and a length of 3-10mm in a plodder, and was dried in an oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 12 for desulfurization, denitrification and CO removal.
Example 13
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co3O4(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: BaO (3 wt.%);
carrier and content: kaolin (13 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 13g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) 5.2g of Ba (NO) is taken3)2Dissolving the mixture into 10g of water, uniformly soaking the mixture in the sample prepared in the step 3), drying the mixture for 2 hours at the temperature of 110 ℃, and then putting the dried mixture into a muffle furnace to decompose the mixture at the temperature of 400 ℃ for 2 hours to obtain the finished product of the novel integrated material 13 for desulfurization, denitrification and CO removal.
Example 14
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co3O4(2wt.％)；
Catalytic component B and content: MoO3(2wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (13 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 6.2g of Mo (NO) are weighed3)3.5H2O, dissolved in 20g of deionized water and uniformly impregnated with 50g of 200 mesh active ingredient Ca (OH)2Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
3) and uniformly mixing the prepared samples 1) and 2) with 13g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 14 for desulfurization, denitrification and CO removal.
Example 15
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(50wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co2O3(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (13 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O，8.2g 50％Mn(NO3)2Solution, dissolving 25gIn deionized water, and uniformly immersed in 25g of 200-mesh active component CaCO3With 50g of 200 mesh active ingredient Ca (OH)2Drying the mixture at 110 ℃ for 2h, and then putting the mixture into a muffle furnace for decomposition at 400 ℃ for 2 h;
2) the sample prepared in 1) was uniformly mixed with 13g of kaolin having a particle size of 200 mesh and 5g of cement having a particle size of 200 mesh, and deionized water in an amount of 40% by weight of the dry matter after mixing was added thereto, followed by kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
3) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 2), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 15 for desulfurization, denitrification and CO removal.
Example 16
The novel integrated material for flue gas desulfurization, denitrification and CO removal comprises the following specific components in percentage by weight:
active components and contents: ca (OH)2(30wt.％)，CaO(20wt.％)，CaCO3(25wt.％)；
Catalytic component A and content: co2O3(2wt.％)；
Catalytic component B and content: MnO2(2wt.％)；
Auxiliary agent and content: TiO 22(3wt.％)；
Carrier and content: kaolin (13 wt.%), cement (5 wt.%).
The preparation method comprises the following steps:
1) weighing 7g Co (NO)3)2·6H2O, dissolved in 15g of deionized water and uniformly impregnated with 25g of 200 mesh active ingredient CaCO3Drying for 2 hours at the temperature of 110 ℃, and then putting the dried material into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours;
2) 8.2g of 50% Mn (NO) was weighed3)2The solution was dissolved in 20g of deionized water and uniformly immersed in 30g of 200 mesh active ingredient Ca (OH)2Mixing with 20g of 200-mesh active ingredient CaO, drying at 110 ℃ for 2h, and then putting into a muffle furnace for decomposition at 400 ℃ for 2 h;
3) and uniformly mixing the prepared samples 1) and 2) with 13g of kaolin with the particle size of 200 meshes and 5g of cement with the particle size of 200 meshes, adding deionized water accounting for 40% of the weight of the mixed dry materials, and kneading in a kneader for 2 hours. And extruding the kneaded sample into a cylindrical strip shape in a strip extruding machine, wherein the diameter of the cylindrical strip shape is 6mm, the length of the cylindrical strip shape is 3-10mm, and drying the cylindrical strip shape in a drying oven at 110 ℃ for 2 hours.
4) And taking 6g of titanyl sulfate solution, dissolving in 6g of slightly acidic water, uniformly soaking on the sample prepared in the step 3), drying for 2 hours at the temperature of 110 ℃, and then putting into a muffle furnace for decomposition at the temperature of 400 ℃ for 2 hours to obtain the finished product of the integrated novel material 16 for desulfurization, denitrification and CO removal.
Example 17
In the embodiment, the service performance of the integrated new material 1-16 for desulfurization, denitrification and CO removal is evaluated, and the evaluation result is shown in Table 1.
A laboratory small-sized fixed bed reaction device is adopted for evaluating the desulfurization, denitrification and CO removal performance, and as shown in figure 1, the device is formed by sequentially connecting a water storage tank 1, a plunger pump 2, ball valves 3 and 15, mass flow meters 4, 6, 8 and 10, pressure reducing valves 5, 7, 9 and 11, a reactor 12, a condenser 13, a needle valve 16 and a three-way ball valve 14 according to the figure, wherein the loading amount of the integrated novel desulfurization, denitrification and CO removal material is 60ml, and the loading height is 50 mm. Four groups of raw material gases NO and SO2CO and O2Are all made of N2The gas as the balance gas enters a mixer after being decompressed and measured, the gas enters a reactor after being fully mixed for reaction, the temperature of the reactor is controlled by adopting an external heating mode, the gas at the outlet is cooled and separated by a cooling separator, and then the gas is measured by a wet meter, one part of the gas enters an infrared flue gas analyzer (GASORD-300) for analysis, and the other part of the gas is directly emptied. The inlet concentration of NO is 300mg/m3，SO2The inlet concentration is 300mg/m3The inlet concentration of CO is 300mg/m3，O2The content is 6 percent, the rest is nitrogen, the flow rate of a water pump is 0.2ml/min, and the air space velocity is 600h-1The reaction temperature is 150 ℃, the reaction pressure is normal pressure and is stableAnd calculating the desulfurization rate, the denitrification rate and the CO removal rate.
Desulfurization rate in terms of SO2The conversion of (a) is calculated by the following formula:
wherein:
is SO2Conversion rate, cSO2 inletIs SO2Inlet concentration, cSO2 outletIs SO2Outlet concentration.
The denitration rate is calculated by the conversion rate of NO, and the formula is as follows:
wherein: etaNOFor NO conversion, cNO inletIs NO inlet concentration, cNO outletIs the NO outlet concentration.
The CO removal rate is calculated as the CO conversion rate, and the formula is as follows:
wherein: etaNOFor CO conversion, cCO inletIs the inlet concentration of CO, cCO outletIs the CO outlet concentration.
Example 18
In the embodiment, the low-temperature service performance evaluation is carried out on the integrated novel material 1 for desulfurization, denitrification and CO removal, the evaluation conditions are shown in the embodiment 15, the reaction temperature is only changed to 110 ℃, and the evaluation results are shown in the table 1. For the embodiments 3, 5, 10, 11 and 12, the novel integrated material for desulfurization, denitrification and CO removal can achieve the same technical effect by changing the reaction temperature.
Example 19
In the embodiment, medium-temperature service performance evaluation is carried out on the integrated novel material 1 for desulfurization, denitrification and CO removal, the evaluation conditions are shown in the embodiment 15, the reaction temperature is only changed to 200 ℃, and the evaluation results are shown in the table 1. For the embodiments 3, 5, 10, 11 and 12, the novel integrated material for desulfurization, denitrification and CO removal can achieve the same technical effect by changing the reaction temperature.
TABLE 1 evaluation result table of integrated new material for desulfurization, denitrification and CO removal
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. The novel integrated material for desulfurization, denitrification and CO removal of flue gas is characterized by comprising 30-80 parts by weight of active component, 0.1-5 parts by weight of catalytic component A, 0.1-5 parts by weight of catalytic component B, 0.1-5 parts by weight of auxiliary agent and 2-30 parts by weight of carrier; the active component is CaCO3With CaO, or CaCO3And Ca (OH)2Or CaCO3With CaO, Ca (OH)2Mixtures of, CaCO3The mass percentage of the active components is 2-50 percent; the catalytic component A is Fe2O3、Co3O4One or more of the above; the catalytic component B is MnO2、CuO、MoO3One or more of the above; the auxiliary agent is MgO, BaO or CeO2、TiO2One or more of the above; the carrier is one or more of kaolin, bentonite, gypsum and cement;
the preparation method of the new material comprises the following steps:
1) dissolving the salt of the catalytic component A in deionized water, and uniformly soaking the salt in an active component CaCO3The active component CaCO loaded with the catalytic component A3Drying and heating for decomposition;
2) dissolving the salt of the catalytic component B into deionized water, and uniformly soaking the salt in active components CaO or Ca (OH)2Or CaO with Ca (OH)2Drying the active component loaded with the catalytic component B on the mixture, and heating for decomposition;
3) uniformly mixing the samples prepared in the steps 1) and 2) with a carrier, adding water, kneading, performing extrusion forming, and drying;
4) and (3) dissolving the salt of the auxiliary agent into deionized water, uniformly soaking the salt in the sample prepared in the step 3), and drying, heating and decomposing to prepare the integrated material for flue gas desulfurization, denitrification and CO removal.
2. The novel integrated material for flue gas desulfurization, denitrification and CO removal as claimed in claim 1, which comprises, by weight, 50-70 parts of an active component, 1-3 parts of a catalytic component A, 1-3 parts of a catalytic component B, 1-3 parts of an auxiliary agent and 10-20 parts of a carrier.
3. The novel integrated material for flue gas desulfurization, denitrification and CO removal as claimed in claim 1, wherein the salts of the catalytic component A, the catalytic component B and the auxiliary agent are nitrates or chlorides; the concentration of the salt of the catalytic component A, the catalytic component B and the auxiliary agent dissolved in deionized water is 0.01-0.5 g/ml.
4. The new integrated material for desulfurization, denitrification and CO removal of flue gas as claimed in claim 1, wherein in step 1) and step 2), the decomposition temperature is 200-500 ℃.
5. The new integrated material for flue gas desulfurization, denitrification and CO removal as claimed in claim 1, wherein in step 3), the extrusion molding is cylindrical strip or cylindrical plum blossom, the diameter is 2-8mm, and the length is 3-20 mm.
6. The new integrated material for desulfurization, denitrification and CO removal of flue gas as claimed in claim 1, wherein in the step 4), the decomposition temperature is 200-500 ℃.
7. The application of the integrated new material for flue gas desulfurization, denitrification and CO removal as claimed in claim 1 or 2, wherein the new material is applied to 100-250 ℃ low-temperature flue gas desulfurization, denitrification and CO removal.
8. The application of the novel integrated material for flue gas desulfurization, denitrification and CO removal as claimed in claim 1 or 2, wherein the novel material is placed in a fixed bed reactor or a moving bed reactor to perform flue gas desulfurization, denitrification and CO removal, and the operating conditions are as follows: 0-5MPa, 100 ℃ and a gas space velocity of 100--1。
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| CN113663504A (en) * | 2021-08-27 | 2021-11-19 | 中晶环境科技股份有限公司 | Desulfurization and denitrification solid particle and preparation method and application thereof |
| CN114931958B (en) * | 2022-06-30 | 2024-01-30 | 太原理工大学 | Coal composite catalyst and preparation method and application thereof |
| CN115869992A (en) * | 2022-12-21 | 2023-03-31 | 山东中移能节能环保科技股份有限公司 | A catalyst for desulfurization and denitrification of coking flue gas and its preparation method |
| CN116920850B (en) * | 2023-07-03 | 2025-03-14 | 河南师范大学 | Multifunctional catalyst applied to medium-low temperature flue gas purification and preparation method thereof |
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